Tissues



tions of amphoteric proteins, whether an alkaline soap is present or not, possess excellent emulsifying and wetting properties, and fats, waxes and similar materials may be emulsifled in the solutions. Thus fats, waxes and the like may be present on the materials being treated when reaction takes place, and it has been found that by this means additional water-repelling properties, as

distinct from waterproof properties, may be obtained, at least temporarily.

In practice, the full waterproofing effect of the process is not shown until the metal-protein compound produced has been dehydratedf thistaking place on drying the material, if. desired at atmospheric temperature. Low temperature drying is especially valuable where delicate fabrics are being treated, for instance fabrics of the substitute type, e. g. paper composites, or fabrics containing cellulose acetate threads, which are liable to bedamaged at high temperatures.

The alkaline solutions of protein containing coloring matter which .may be used according to the invention are suitably prepared in a concentrated form and diluted for use. The concentrated solutions are well iitted for storage.

A suitable method of carrying out the process of the invention is to dissolve or suspend the coloring matter in a solution of the amphoteric protein or the metal compound, or in a solution of both reagents, and to pad, dye, print, stencil or spray fabric or yarn with the product, reaction being subsequently effected as described above. By the adoption of such a treatment not only is the self dyed or printed 'eect accomplished with a great saving of coloring matter and at a vastly higher speed than is usual by ordinary methods of coloring, but the dyer or printer is rendered completely or almost completely independent of the specific properties which usually confine certain coloring matters to certain fabrics. The reaction may be carried out practically in the cold, and without the necessity of special preparation of the fabric. Thus, for example, fabrics imported from the East or elsewhere, e. g. Japanese silks, may be colored without necessarily removing the manufacturers finish, and

consequently many expensive operations now necessary in the coloring of such imported products may be eliminated.

The method of application should be varied in accordance with the type of dyeing or printing to be adopted. In general, for self-colored goods the most advantageous method is to pad the goods in open width through a protein-metal compound-color mixture, remove the excess of the mixture by rollers or by suction, run the impregnated cloth in open width into the acidifying solution, for example a 1-6% solution of acetic,

formic or oxalic acid, and then after removal of excess liquor to run the cloth through water to remove the remaining free acid. The material is .then dried and finished. If a volatile acid is employed the fabric may be dried direct and the washing operation omitted. In this manner a `silk fabric, for example, may be dyed an even shade of an acid color equivalent in intensity at least to that obtained by a double amount of the same color dyed in the ordinary way upon lthe same cloth. Moreover, if desired the treatment may be carried out at atmospheric temperature and continuously at a rate up to 120 to 130 linear yards per minute. The same acid color may be applied in the same way to yarns or fabrics. woven or knitted, of cotton, linen. viscose manner.

or acetate rayon, wool or, indeed, to any yarns or fabrics, though as is well known many of these materials are not dyed at all by acid colors by the ordinary processes of dyeing. Similarly, basic or direct colors may be applied to all types of fabrics and yarns independently of their substantivity or otherwise. It is also possible to attach insoluble colors and pigments to the fibre similarly, for instance by suspending them in a protein-metal mixture which is applied to the materials being treated.

Since by the treatment the materials are colored and waterproofed simultaneously, they do not bleed in water, notwithstanding the lack of substantivity of the color to the ilbre in some cases. Moreover the materials will endure cleaning with volatile solvents such as White spirit or benzene.

Where it is desired to color a portion only of a material, as for instance in printing, by roller, block, stencil or screen, or aerograph or by any of the recognised methods employed, it is advantageous in general to cause the necessary acid conditions to be set up either by passing the material after it has been printed with an alkaline protein-metal compound-color medium through acid vapor or through acidified steam, acidiiled for example with acetic acid, or to incorporate in the printing paste bodies which, when the printed material is dried, will generate by their decomposition the necessary acidi The invention is illustrated by the following examples:

Example 1 r11/2 lbs. of oleic acid are mixed with r11/2 lbs. of hard parailin scale, and the mass is treated with a quantity of strong caustic soda solution (for instance a 20% solution) sufficient to convert the oleic acidv into soap. A solution of 8% lbs. of casein and 21/2 lbs. of borax in 45 lbs. of water is then added in a steady stream with continuous stirring. The homogeneous product is diluted with water to lbs. weight, when a homogeneous cream very suitable for storage is obtained. 10 lbs. of this cream are diluted with 140 lbs. of a 1% solution of an acid dyestuff, e. g. Naphthalene Red, or a direct dyestuff, e. g. Benzo Sky Blue, or of a $/4% solution of a basic dyestui, e. g. Methylene Blue DBB, and the mass is mixed to give a homogeneous solution. Through this solution a cloth, lor instance of silk, wool or cotton, is padded, preferably in a three-roll padding machine of the usual construction. A high velocity of treatment, for instance up to linear yards per minute, may be employed. 0n emerging from the padding machine, in which excess of liquor has been removed from the treated materials, so that they contain about their own weight of liquor, the materials are passed directly in open width through a second padding machine, where they come into contact with a solution of aluminium hexaacetate or hexaformate of about M5 N. strength, this solution being if desired rendered slightly more acid by the addition of acetic or formic acid. From this padding machine the goods are passed directly through a drying stenter.

The finished product possesses water-repelling properties, and the shade developed is more intense than would have been obtained by dyeing with the same amount of dyestuif in the usual Example 2 7 1/2 lbs. of tallow fatty acids are mixed with 6 accuses lbs.. oi paraffin scale, and the mass is treated with lid tid

concentrated aqueous caustic-potasio. While the soap produced is still molten, a solution of 10 lbs. oi casein and 3 lbs. of decahydrated borax inv 100 lbsfoi water is added withl stirring, and when a homogeneous liquorl has been formed it is allowed'to cool. 3.36 lbs. of sodium aluminate (52 to 53% A1203. 42.5% Nano) are then mixed with the mass, and a product in a satisfactory condition lor storage and having a' pH. value of 10 or more is obtained. 10 lbs. of this product are then coined with 140 lbs. of dyestufl solution, e. g. a`

%% solution of an acid or direct dyestuii or a lt/% solution of a basic dyestui, and textile mav'nnantlty oi dyestui when this dyestuff is applied dit fdd

dit

llt

by the usual methods of dyeing.

Exemple 3 'the paste produced as described at .the beginning ci Example 2 and referred to as having a pli value of 10 or more is mixed with a solution or an acid, direct or basic dyestuff in the proportions oi two parts of the paste to one .of dyestuil solution. The dyestud solution may suitably be oi such a concentration that the product contains, lor example, 1% o1' an acid or direct dyestnd or t/.l% of a basic dyestuff.- The mixture produced 4is used directly asa printing paste lor the production of screen prints upon Japanese silk web in its raw state as received by the importer. The screen printed piece is passed directly after printing through a low pressure steamer, in which the steam vapor has been ren tiered acid by the introduction of a volatile acid such as acetic or iormic acid, the temperature being such that 'the goods do not become wet. diront. this steamer the goods are passed at once to drying and calendering.

The intensity of shade so developed is equal to that developed by at least three times the quantity oi dyestuii employed when the goods ,are

dyed by normal processes.

Example 4 tdt lbs. oi casein are mixed with 2.5 lbaoi 4decahyrlrated borax and the mixture is fed4 with constant stirring into 90 lbs. of water. When the mass is homogeneous, 15 lbs. 'of commercial soap naires are added slowly and the stirring is continued, water being added until the whole nicos weighs about 100 lbs. and is homogenous. l 'The mixture is then cooled or allowed to cool.,

preferably with stirring, and -a solution of 4 lbs.

olsodium aluminate in 40 lbs. of water is added. /llllien the product is cold, a solution oi l5 lbs. oi pyridine osalate or acetate or ammonium onnlnte or acetate4 in 400 lbs. -of water m added. The parte obtained is mixed with a solution of un ncld, `direct or basic dyestilin the proportions tufo parte ot paste to one of solution, the solution ot dyestulll being sutiiciently concentrnted to give n final nur.' containing tor example l% oi on acid or direct dyestui or 344% oi a basic dyestun. v

'll'lle product is employed for block printing calico in the usual way. After printing, the nieces are immediately dried, for` instance ori "tins at a steam pressure oi id lbs. per square inch gauge, or in a stove.

The heating step completesftlifdperation, and the colored product s "sses at least three times as deep a shade as wenn. be produced with the same amount of `dyestui used in ordinary processes. 'In addition, the pattern .is waterprooi.

Example 5 To l lbs. of the product obtained in the manner described at the beginning of Example 4, after. the addition of the pyridine oxalate or acetate or ammonium oxalate or acetate, there are added 140 lbs. of a 1% solution ol an acid dyestu, e. g. Naphthalene Red, or a direct dyestufi, e. g. Benzo Sky Blue, or of a 43% 'solution of a basic dyestuilf, e. g. Methylene Blue DBB,

and the mass is mixed to give a homogeneous solution. Through this solutiona cloth, for' instance of silk, wool or cotton, is padded, preterably in a three-roll padding machine of the usual construction. A velocity of treatment up to 12d i linear yards per minute may be employed. 0n

emerging from the padding machine, `in which excess of liquor has been removed from the treated materials, so that they contain about their own weight oi liquor, the products are passed in open width to drying tins supplied with steam at a pressure of l0 lbs.l per square inch gauge, or to a stove, and are dried.

Eaomple t To the lull lbs. or homogeneous cream produced as described at the beginning of Example i are added 11/2 lbs. of an arylide or 2.3-hydroxynaphthoic acid, for instance the' anillde sold under the registered trade-mark Brenthol A. 8., and the materials are well pasted together. To this paste is added 1,400 lbs. oi water at a temperature of about 4u C., the addition being made gradually and the paste being worked to give as homogeneous a `product as possible. Cotton cloth is padded through such a mixture, for instance through a three-roll padding machine, preferably to give a product containing about its own weight ci liquor. The goods are then passed in open width to asecond padding machine containing the customary developing solution, for y instance a solution of diazotised m-nitro-ptoluidine in an equivalent concentration to that of the arylide in the iirst bath, there having been added to the developing solution sumcient alumlnlum hexaiormate r hexaacetate to form in i the diano solution a 1/ 15N. concentration of the hexe. salt. The goods on leaving the developing bath are run in open width through a .washing machine, and are dried, stentered and nished in the usual Way.

The color so produced is especially fast to rubhing. 'This is a great advantage, for it is Well known that colors ol the hydroxynaphtholc acid arylide group are normally unsatisiactory when subjected to rubbing.

I claim:

1. A process for the productlonrolJ colored, waterprooled textile 'and like materials, which comprises causing an extremely dilute solution comprises impregnating the individual fibres of the material in the cold with a non-acid solution of an amphoteric protein and causing the protein to react with a solution of a compound containing an amphoteric metal on the material and under acid conditions and in the presence of a coloring matter to develop an insoluble colored complex within the bre.

3. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual bres of the material in the cold with a non-acid solution of an amphoteric protein and then treating the impregnated material, in the presence of a coloring matter, with an acid solution of a compound containing an amphoteric metal, to develop an insoluble colored complex within the fibre.

4. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual fibres of the material in the cold with a non-acid solution of an amphoteric protein, treating the impregnated material with a non-acid solution of a compound containing an amphoteric metal, and then rendering the material acid in the presence of a coloring matter, toA develop an insoluble colored complex Within the fibre.

5. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual fibres of the material in the cold with a non-acid solution of an amphoteric protein and a compound containing an amphoteric metal, said solution containing a coloring matter, and then rendering the impregnated material acid, to develop an insoluble colored complex within the bre.

6. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual libres of the material in the cold with a non-acid solution of casein containing a coloring matter, and then treating the impregnated material with an acid solution of a compound containing an amphoteric metal, to develop an insoluble colored complex within the bre.

7. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual bres of the material in the cold with an alkaline solution of casein of a pH value of about 10, containing a coloring matter, and then treating the impregnated `material with an acid solution of a compound containing an amphoteric metal, to

develop an insoluble colored complex within the libre.

8. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual fibres of the material in the cold with an alkaline solution of casein and causing the casein to react with an aluminate on the material under acid conditions and in the presence of a coloring matter to develop an insoluble colored complex within the bre.

9. A process for the production of colored, waterproofed textile and like materials, which comprises impregnating the individual bres of the material in the cold with an alkaline solution of casein and causing the casein to react with an organic aluminum salt on the material in the presence of a coloring matter to develop an insolublecolored complex within the fibre.

101 An impregnated textile material having developed within the fibre so much of an insoluble colored complex containing a coloring matter and the product of the reaction between an amphoteric protein and a compound containing an amphoteric metal, that the material is colored and rendered waterproof but substantially retains the remaining initial qualities of the material as such.

l1. An impregnated textile material having developed within the bre so much of an insoluble colored complex containing' a coloring matter and the product of the reaction between casein .and a compound containing an amphoteric metal,

that the material is colored and rendered waterproof but substantially retains the remaining initial qualities of the material as such.

12. An impregnated textile material having developed within the fibre so much of an insoluble colored complex containing a colored matter and the product of reaction between casein and aluminium hexa-formate, that the material is colored and render Waterproof but substantiallyy 

